N heterocyclic ethyl naphthalimides

ABSTRACT

The present invention is directed to novel naphthalimide derivatives which have been quaternized or made into a salt form and a method for preparing the same. The present compound is used in fluorescent whitening of various synthetic fibers, particularly polyacrylonitrile fibers.

ilnitn States atent Inventors Tamehiko Noguchi Tokyo;

Mitsukuni Sumitani, Soka-shi; Kenkichi Tsuitamoto, Yono-shi; Daisaku Matsunaga, lUrawa-slhi, all 011 Japan Jan. 23, 1968 Dec. 7, 1971 Nippon Kayaku Kabushiko Kaisha Tokyo, Japan Jan. 30, 1957 Japan Feb. 3, 1967, Japan, No. 42/6590; May 10, 1967, Japan, No. 42/2911]; Sept. 2, 1967, Japan, No. 42/561184 App]. No. Filed Patented Assignee Priorities N HETEROCYCLIC ETHYL NAPHTHALIMIDES 6 Claims, No Drawings 11.5. C1 260/2811, 8/55, 252/3012 W, 26/37 NP, 260/247.5,

260/487, 260/561 AL, 260/583 P [51] Int. Cl C07d39/00 [50] Field of Search 260/281 [56] References Cited UNITED STATES PATIENTS 3,310,564 3/1967 Kasai 260/281 3,330,834 7/1967 Senshu 260/281 FOREIGN PATENTS 24910 10/1965 Japan 260/281 14988 7/1964 Japan 260/281 21127 11/1964 Japan 260/281 Primary Examiner-Donald G. Daus Artorney-Birch,Swind1er, McKie & Beckett ABSTRACT: The present invention is directed to novel naphthalimide derivatives which have been quaternized or made into a salt form and a method for preparing the same. The present compound is used in fluorescent whitening of various synthetic fibers, particularly polyacrylonitrile fibers.

N HETEROCYCLIC ETHYL NAPHTHALIMIDES This invention relates to a novel naphthalimide having the following general formula,

' wherein R represents Sii i'r'bub substituted with hydroxyl group, alkoxy group, phenoxy or phenyl group; n represents an integer of 2 or 3; X represents a substituent group of v wherein R and R represent the same or different alkyl groups, substituted alkyl group or alicyclic group, or R and R represent a ring formed by connecting each with other together with an amino group nitrogen, and R represents a hydrogen atom or residual group of quatemizing agent, or

wherein R represents a hydrogen atom or residual group of quaternizing agent and R represents a hydrogen atom or alkyl group, or

wherein R, represents a hydrogen atom or residual group of quaternizing agent and R represents an alkyl group, phenyl group, or substituted phenyl group; and Y represents an anion.

The present naphthalimide derivative is used in the fluorescent whitening of various synthetic fibers such as polyvinyl alcohol polyamide fibers, and polyacrylonitrile fibers, and semisynthetic fibers such as cellulose acetate more particularly used in the fluorescent whitening of polyacrylonitrile fibers.

Alkoxynaphthalimide derivatives have been heretofore used as a fluorescent whitening agent and their excellent whitening effect on the polyester synthetic fibers and polyacrylonitrile fibers has been widely recognized (US. Pat. No. 3,310,564). However, these compounds are sparingly soluble in water, and thus to disperse these compounds into water, a dispersing agent must been used. Further, when the thus dispersed compounds are applied to the polyacrylonitrile fibers, their adsorption ratio is low, the whiteness effect is low, and the various fastnesses of whitened article are not suffi ciently good.

As a result of the studies on the present compound as shown in the above general formula I, the present inventors found that said various disadvantages can be eliminated by using the present compounds. That is, the present compound as shown in the above general formula I is very readily soluble in water and requires no dispersion treatment using a dispersing agent when applied. Further, the adsorption ratio is much improved, so the loss of the compound itself into the both can be prevented after the treatment. Furthermore, the whitening effect is considerably improved. It is also notable that the various fastnesses of the cloth whitened with the compound as shown in the above general formula I, particularly the light fastnesses, the most important property required for the fluorescent whitening agent, are remarkably improved, as

wherein n, R R R and R have the same meanings as defined above, whereby naphthalimidet-sulfonic acid or its salt represented by the following general formula 5, 6 or 7 is obtained correspondingly,

wherein R R R,,, R,, and n have the same meaning as defined above.

The resulting compound is then subjected to reaction with an alcohol as represented by the following general formula 8, or its alcoholate R 13 OH 8 in the presence of a condensing agent, whereby compound as represented by the following general formula 9, l0 or 1 l is obtained correspondingly,

wherein R,, R R R R and n have the same meaning as defined above.

In the present condensation reaction, an alkaline condensing agent is generally used as a condensing agent, but the particularly preferable condensing agent is a hydroxide of alkali metal, such as sodium hydroxide or potassium hydroxide. The present condensation reaction can be favorably carried out when the alcohol as represented by the above general formula 8 is used as a diluent, but sometimes the condensation reaction can be also carried out in a suitable inert solvent. The necessary reaction temperature and reaction time vary depending upon the kind of alcohol and the kind and quantity of alkali used. The reaction can be generally carried out at a temperature of 50 to 150 C.

Then, the resulting condensation compound is treated with a quaternizing agent or is subjected to addition reaction with a known inorganic or organic acidic compound capable of forming a salt with the amine as represented by the general formula 9, 10 or ll, whereby the compound represented by the general formula 1 is obtained.

ll. The compound as represented by the general formula 1) can be also prepared in the following manner:

4-hydroxynaphthalic acid, its anhydride, or their salt is subjected to reaction with an alkylating agent such as dialkyl sulfate, p-toluenesulfonic acid alkyl ester, etc. according to the conventional method, whereby 4-alkoxynaphthalic acid anhydride as represented by the following general formula 12 is obtained,

wherein R has the same meaning as defined above. The resulting 4-alkoxynaphthalic acid anhydride is subjected to reaction with an amine as represented by the above general formula 2, 3 or 4, whereby the compound as represented by the above general formula 9, 10 or 1 1 can be obtained. Then, the resulting compound is quaternized or made into a salt form in the same manner as in l, whereby the desired compound is obtained.

The compound as represented by the above general formula 2 and used in the synthesis includes di-substituted aminoalkylamine such as B-dimethyaminoethylamine, B- diethylaminoethylamine, B-diisopropylaminoethylamine, B- di-n-amylaminoethylamine, B-diethanolamineothylamine, B- ethylethanolaminoethylamine, B-methylmpropylaminoethylamine, B-cyclopentylmethylaminoethylamine, y-dimethylaminopropylamine, 'ydiethylaminopropylamine, y-di-n-butylaminopropylamine, and 'y-cyclohexylmethylaminopropylamine, and further includes morpholinoethylamine, morpholinopropylamine, piperidinoethylamine, piperidinopropylamine, pipecolinopropylamine, piperidinoethylamine, pyrrolidinoethylamine, pyrrolinoethylamine, etc.

The compound as represented by the general formula 3 includes 2-B-aminoethylpyridine, 4-B-aminoethylpyridine, 2-8- aminoethyI-S-ethylpyridine, 3-B-aminoethyl-6-methylpyridine, etc.

The compound as represented by the above general formula 4 includes l-'y-aminopropyl-2-ethylimidazole, 1-yaminopropyl-Z-methylimidazole, l-B-aminoethyl-2- ethylimidazole, l-'y-aminopropyl-2-phenylimidazole, l-(B- aminoethyl)-2-methylimidazole, etc.

The alcohol as represented by the above general formula 8 includes methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, tert.-butanol, n-amylalcohol, i-amylalcohol, benzylalcohol, B-phenylethylalcohol, y-phenylpropylalcohol, ethylene glycol, propylene glycol, ethylene glycol monobutylether, ethylene glycol monomethylether, ethylene glycol monoethylether, ethylene glycol monophenylether, propylene glycol monomethylether, propylene glycol monophenylether,

The quaternizing agent used in quaternizing the compound as represented by the above general formula 9, l0 or I l includes alkyl halide such as methyl chloride, methyl iodide, ethyl iodide, methyl bromide, ethyl bromide, propyl bromide, n-butyl bromide, isobutyl bromide, dodecyl bromide, etc., aralkyl halide such as benzyl chloride, etc.; a-halocarboxylic acid derivative or B-halocarboxylic acid derivative such as chloroacetamide, ethylchloroacetate, B-chloropropionamide, ethyl B-chloropropionate, B-bromopropionamide, ethyl [3- bromopropionate, etc.; dialkylsulfate such as dimethylsulfate, diethylsulfate, etc.; arylsulfonic acid alkyl ester such as benzenesulfonic acid methyl ester, toluenesulfonic acid methyl ester, toluenesulfonic acid ethyl ester, toluenesulfonic acid n-butyl ester, etc., alkylsulfonic acid alkyl ester such as methanesulfonic acid methyl ester, butanesulfonic acid ethyl ester, etc.; acid halide such as methanesulfonyl chloride, ethanesulfonyl chloride, butanesulfonyl chloride, toluenesulfonyl chloride, acetyl chloride, etc., and aliphatic sultone such as propanesultone, butanesultone, etc., and haloamine such as chloramine etc.

The acidic compound used in the formation of a salt of the compound as represented by the general formula 9, l0 or I l includes inorganic acid such as hydrochloric acid, hydrobromic acid, hydriodic acid, sulfuric acid, phosphoric acid, perchloric acid, periodic acid, etc., and organic acid such as benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid, phenolsulfonic acid, naphthalenesulfonic acid, naphthalenedisulfonic acid, naphthalenetrisulfonic acid, formic acid, acetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, etc.

The present compound as represented by the general formula l is readily soluble in water, and clearly whitened cloth of polyacrylonitrile fibers having a high light fastness can be obtained by treating said cloth in an acidic bath containing the present compound. In treating the polyacrylonitrile fibrous material the material may be optically whitened by treating the same with the compound as represented by the general formula I, after bleaching the same with a bleaching agent such as sodium chlorite at first and then dechlorinating the bleached material with sodium bisulfite, or the material may be optically whitened by simultaneously using the compound as represented by the general formula 1 and a bleaching agent such as sodium chlorite, or a suitable surface active agent or a dyeing assistant. Further, it is also possible to prepare the fluorescently whitened filaments by directly adding the present compound to the polyacrylonitrile spinning solution. Furthermore, a remarkable whitening effect can be also obtained when the present compound is used in the fluorescent whitening of the synthetic resin or plastics containing polyacrylonitrile.

The amount of the present naphthalimide compound used in the whitening can be varied in a wide range, depending upon the desired whiteness and the material to be whitened, but actually a remarkable whitening effect can be obtained even when 0.0l-O.5 percent by weight of the present naphthalimide compound is used.

The following examples are given merely as illustrative of the present invention and are not to be considered as limiting. in the examples, part and percentage are by weight.

EXAMPLE 1 Thirty parts of sodium naphthalic acid-4-sulfonate are added to a mixture consisting of 166 parts of water and l8.4 parts of l-y-aminopropyl-2-ethylimidazole and subjected to reaction for 3 hours at C. After the completion of the reaction, the resulting product mixture is weakly acidified with hydrochloric acid, and the resulting deposited white crystals are filtered off, washed with water and dried, whereby a compound as represented by the following formula l3 is obtained.

Ten parts of the thus obtained compound are added to a mixture consisting of l50'parts of methanol and I parts of caustic soda and subjected to reaction for 2 hours under reflux. After the completion of the reaction, the resulting product mixture is put into 600 parts of water, and the resulting deposited crystals are filtered off, washed with water and dried, whereby a compound as represented by the following formula 14 is obtained.

When 10 parts of the compound as represented by the formula 14 are suspended in 50 parts of ethanol, 10 parts of concentrated hydrochloric acid are added thereto and the resulting mixture is left at room temperature for 1 hour, the crystals are deposited. The resulting crystals are filtered off, washed with acetone and dried, whereby a compound having a melting point (decomposition of 231 C. as represented by the following formula 16 is obtained.

EXAMPLES 2-49 Sodium naphthalic acid-4-sulfonate is imidized with the amine as represented by the general formula 2, 3 or 4 and shown in the following table I, then subjected to reaction with alcohol as represented by the general formula 8 and quaternized with a quaternizing agent or made into a salt form with an acidic compound according to the same procedure as described in example l.

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Product c Sameasabove H7030 N(CH2)2 N(CH2)3N H CH: .00

Amine cgrgrourid as I re resen e y ormu a Quaternizing agent or Alkylatmg agent (25 (3) 0r (4) acidic compound t do CH3 S OaC3 1 (CH )2S04 /CH3 HzS04 NH2(CH2) 3-N 3 Oily state (ordinary temperature).

EXAMPLE 87 0.4 part of the compound prepared in example 68 is dissolved in 3000 parts of water, and. 5 parts of sodium 5 hypochlorite, 2.5 parts of chlorous dioxide gas generatipn inhibitor and 5 parts of acetic acid are thereto added. One hundred parts of polyacrylonitrile fabrics are dipped in the resulting bath at 70 C., heated to 100 in 20 minutes. treated for 1 hour at this temperature and then cooled to 70 C. After the dechlorination treatment with an aqueous sodium bisulfite solution at 70 C. for 20 minutes, the fabrics are washed with water and dried, whereby whitened fabrics having a very high light fastness are obtained.

Even if the compound prepared in examples 9, 10, 26, 27 or 67 is used in place of the compound as prepared in example 68, whitened fabrics having a very high light fastness can be likewise obtained.

EXAMPLE 88 0.2 part of the compound as prepared in example 1 is dis 2O solved in 3,000 parts of water, and 5 parts of formaldehyde sodium sulfoxylate and 5 parts of acetic acid are thereto added. A mixed spun cloth of polyacrylonitrile-wool (50:50)

is dipped in the resulting bath at 60 C, heatedto 96 C. in

minutes, treated at this temperature for 40 minutes, cooled to 70 C., washed with water and dried, whereby the clearly whitened cloth is obtained 0 Even if compounds as represented by the following formulas are used in place of the compound as represented by the formula 15, clearly whitened cloth can be likewise obtained.

(xm: 380 mu; Fl 484 mu) 5 AMI-I (Men: 380 mu; Fla: 484 mp) EXAMPLE 89 Thirty parts of acrylonitrile polymer are dissolved in l00 parts of dimethylformamide at 90 C., and 0.] part of the com pound as represented by the formula 18 is thereto added. The thus prepared spinning solution is extruded from spinning nozzles into 100 parts of water and coagulated at 20-30 C.

Then, the coagulated filaments are stretched five times as long as 80 C., washed with water, treated with a textile auxiliary agent, and dried, whereby fluorescently whitened, clearly white polyacrylonitrile filaments are obtained.

Even if the compounds having the following formulas are used in place of the compound as represented by the formula l8, the similar result can be obtained.

0.4 part of the compound is dissolved in 3,000 parts of EXAMPLE 92 water. I00 parts of vinylon cloth are dipped into the thus prepared bath, heated to 90 C. in 20 minutes, treated at that temperature for 1 hour, washed with water, and dried,

I whereby clearly whitened cloth is obtained.

CH3SO3 EXAMPLE 93 (OHM Two aqueous bleach bathes are prepared separately accorde3 ing to the following formulations for the purpose of comparison: (Mm: 381 mu; Flo": 485 mu) 3 The conventional bath: C O 4 mcthoxynaphthalic methylimide. percentage on n-C4HnO 5 the weight of fiber 0.4%

9 Bath ratio 1 :30 /N (CH2): CHaso (b) The present bath:

CHa A compound as represented by the general formula I,

ie H3 CH3 (7\ 2383 my; Fl :472m

where R1: CHa, n: a, x; N-OH3, Y: 02115804,

i- CO GHrSOi 02H;

H0ciH,-0 v.

percentage on the weight of fibers 0.4% N (CH2): \N Bath ratio 1:30 l CO CH; m-r 380 u; lmu 7 ii) The thus prepared bathes are adjusted to a pH of 3 by ad- /C0 ding thereto acetic acid. Polyacrylonitrile fibers are dipped in an equilibrium.

\ these bathes respectively. When the bathes are maintained at /N-(CH2)2 gaCzH5 I 90 C. for 60 minutes, adsorption of whitening agent reaches 00 Percentage equilibrium adsorption is calculated as a ratio of (Mn- 2378111); Flo 467m optical density of original bath to that of the bath after treat- F C 0 I ment. The percentage equilibrium adsorption for these two HzCO H bathes are shown below:

N-(CHr)z-N H8049 Bath Percenta c e uilihrium adsor lion H CH3 a g 41. p

EXAMPLE 90 Ten parts of acrylonitrile polymer and 0.04 part of the com- EXAMPLE 94 pound prepared in example 5 are dissolved in 100 pans of Two aqueous bleaching bathes are prepared separately ac dimethylfonnamide at 90 C. A proper amount of the resulting cording to the following formulations for the purpose of comsolution is poured onto a glass plate to form a film by means of parison: an applicator, and then dipped into water immediately to deposit the resin. The thus obtained film is then dipped into (3) Conventional hath: hot water at 60 C. to sufficiently remove the solvent, washed 4-rneih rynu hihalic mclhylimide, percentage on with water and dried, whereby a fluorescently whitened, S "F" odium hypochloritc. percentage on clearly white film of polyacrylonitrile polymer is obtained. he will, or fibers I 0% The heat resistance in organic solvent of the compound Chlorous dioxide gas generation inhibitor, used in this example is very excellent. 'f ll Bath ratio I130 EXAMPLE 91 (b) Present bath:

0.4 part of the compound prepared in example 2 is dissolved The compound as represented by the general formula l into 3,000 parts of water, and 100 parts of acetate cloth are dipped into the thus prepared bath, heated to 85 C. in 20 minutes, treated at this temperature for 45 minutes, washed 60 CH; with svater and dried, whereby clearly whitened cloth is obwherein R1: GH8 n: 31X: I and tame Even if a compound as represented by the following formu- I lav Y: CH,SO,. percentage on the weight of fibers 0.4 or 0.5%

65 Sodium hypochloritc. percentage on C O the weight of fibers IO'Z Chlorous dioxide gas inhibitor, percentage on Q N N H e the tight oflibers 5% Bath ratio 00 w The thus prepared bathes are adjusted to a pH of 3.0 by adis used in place of the compound used in this example, clearly ding thereto acetic acid. Polyacrylonitrile spun fabrics are whitened cloth can belikewise obtained. dipped separately into these bathes at 50-60 C. The bath temperature is raised up to 98-l00 C. for 40 minutes and then gradually cooled down to 70 C. I

The treated fabrics are washed with water, treated with an 9 aqueous sodium bisulfite solution (1 g./l.) at 6070 C. for l (CH2)? S 03 minutes and then washed with water. in this manner, the a) whitening (optical brightening) and chemical bleaching treat- 7 H3 ments are effected simultaneously.

The thus treated fabrics have the following whiteness: 3. The compound according t0 c|alm in lhe 1 2 value i a mean value f4 values measured 0 pound IS represented by the following formula:

A2 (Z-value of treated fabrics) (Z-value of nontreated fabrics) C 0 5 Compound l C 0 Compound as represented by A m V t e general formula:

9 6 (Rx: CH2, 11:3, X:NCH3 (CH2)2 N-CHS CHQS O4 4-methoxynaphthallo 02H: methyllmide and YZGiHfiSOl) Item Z value AZ value Z value AZ value Concentration 4. The compound according to claim 1, wherein the com- 0 F pound is represented by the following formula;

Non-treated Iabrl /N(CH2)z \\N$ 2. Hunter-L, a, b system \CO 1'1 K V'l-( V-I-( VI (a mean value of 4 values measured) Compound Compound as represented by the general ormula:

(RIICHg, m3, X:NCH;

C2115 i-methoxy-naphthalic methylimide and Y: 0211 804) Item L a b AE L a b AE Concentration (O.W.F.)

Non-treated fabrics- 94.6 1.6 +5.1 94.6 1. 6 +5.] 04 u 97 4 +3.91 17.0 12.2 97. 27 +4.1 l7.9 13 6 75 17 25 12.7 97 5 +4.0 +18.5 13 5 Measurement is carried out by means of a xenon automatic 50 5. The compound according to claim ll, wherein the comfluorescence color difference meter using the whitened fabrics pound is represented by the following formula: after ironing the fabrics at l40-l C.

What is claimed is: l. A compound as represented by the formula,

. /CO\ e \Nwn) cnasol 00 R10"' Q /N(CH2) R5 Y 00 CH3 6. The compound according to claim 1, wherein the compound is represented by the following formula,

wherein R is a lower alkyl group, a lower alkoxyethyl group, a phenylethyl group or a phenylpropyl group; R. is a hydrogen atom, a lower alkyl group or benzyl group; R is a hydrogen CO atom or a lower alkyl group; and Y is a colorless anion. H 0 0- 2. The compound according to claim 1, wherein the com i pound is,represented by the following formula:

UNITED STATES PATENT OFFICE CERTIFICATE 0F CORRECTEQN Patent No. 3,625,94 Dated Dee ember "r, ls'rl Nnguchiei; 3,1

It, is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

On the cover sheet ["5 3] the assignees name "Kabu'shiko" should read w Kabushiki [32] under Priorities, "Jan, '30, 1957" should read Jan. 30, v196? column2, line 54, "12 130H8" should read R OH at the end of line 5- insert ---'(8) column 12, 7 Example 28, under. Pr' t. within the Formula:

"N(C )3 N the'B"shou1dbe "m"; column 19, figure, 1?, "0C" shouldrcao column 22, Figure 6l, last column, "46" shouldlr'ead Q68 Signed and sealed this 26th day of December 1972.

(SEAL) Attest: I

EDWARD M.FLETC ERJR. ROBERT GOTTSCHALK v Attesting Officer -Gox'nmzLssioner of Pateni FORM PO-1050 (10-69) I USCOMM'DC m, I U.$ GOVERNMENT PRINTING OFFICE: I965 O-356"334, 

2. The compound according to claim 1, wherein the compound is represented by the following formula:
 3. The compound according to claim 1, wherein the compound is represented by the following formula:
 4. The compound according to claim 1, wherein the compound is represented by the following formula;
 5. The compound according to claim 1, wherein the compound is represented by the following formula:
 6. The compound according to claim 1, wherein the compound is represented by the following formula, . 